Herein, we report stoichiometric investigations embodying the first highly enantioselective aryl-aryl coupling facilitated by a gold complex. With up to 91% ee, this is the first demonstration of a transmetalation and C(sp2)-C(sp2) reductive elimination sequence with high enantioselectivity using a gold complex. The results offer a basis for development of enantioselective gold-catalyzed aryl-aryl coupling reactions.